Crystal structure of (Z)-3-benz-yloxy-6-[(2-hy-droxy-5-methyl-anilino)methyl-idene]cyclo-hexa-2,4-dien-1-one.

In the title Schiff base compound, C21H19NO3, the conformation about the C=C bond is Z. The N-H group and carbonyl O atom form an intra-molecular N-H⋯O hydrogen bond with an S(6) ring motif. The benz-yloxy ring and the 2-hy-droxy-5-methyl-phenyl ring are inclined to the central six-membered ring by 13.68 (9) and 9.13 (8)°, respectively, and to one another by 21.95 (9)°. In the crystal, mol-ecules are linked by O-H⋯O hydrogen bonds, forming helical chains along [010].

Related literature

For some general background on Schiff bases and their various biological activities, see: Arora et al. (2002 ▶); El-Masry et al. (2000 ▶); Jarrahpour & Khalili (2006 ▶); More et al. (2001 ▶); Phatak et al. (2000 ▶). For related structures, see: Akkurt et al. (2005 ▶, 2008 ▶). For pharmaceutical and industrial applications of azomethines, see: Prakash & Adhikari (2011 ▶). For the effect of hydro­philicity on drug properties, see: Lin & Lu (1997 ▶).

Experimental

Crystal data

C21H19NO3

M = 333.37

Monoclinic,

a = 12.594 (5) Å

b = 9.303 (5) Å

c = 14.997 (5) Å

β = 96.402 (5)°

V = 1746.1 (13) Å3

Z = 4

Mo Kα radiation

μ = 0.09 mm−1

T = 293 K

0.03 × 0.02 × 0.01 mm

Data collection

Bruker APEXII CCD diffractometer

19603 measured reflections

5148 independent reflections

2672 reflections with I > 2σ(I)

R int = 0.037

Refinement

R[F 2 > 2σ(F 2)] = 0.050

wR(F 2) = 0.158

S = 1.01

5148 reflections

238 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.22 e Å−3

Δρmin = −0.16 e Å−3

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2006 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814016936/su2761sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814016936/su2761Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814016936/su2761Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S1600536814016936/su2761fig1.tif

View of the mol­ecular structure of the title mol­ecule, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

Click here for additional data file.

b . DOI: 10.1107/S1600536814016936/su2761fig2.tif

Partial view along the b axis of the crystal packing of the title compound, showing the hydrogen bonds as dashed lines (see Table 1 for details).

CCDC reference: 1015522

Additional supporting information: crystallographic information; 3D view; checkCIF report

C21H19NO3	Z = 4
Mr = 333.37	F(000) = 704
Monoclinic, P21/c	Dx = 1.268 Mg m−3
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 12.594 (5) Å	µ = 0.09 mm−1
b = 9.303 (5) Å	T = 293 K
c = 14.997 (5) Å	Block, orange
β = 96.402 (5)°	0.03 × 0.02 × 0.01 mm
V = 1746.1 (13) Å3

Bruker APEXII CCD diffractometer	2672 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.037
Graphite monochromator	θmax = 30.2°, θmin = 2.6°
phi and ω scans	h = −17→17
19603 measured reflections	k = −13→13
5148 independent reflections	l = −21→20

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.158	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ2(Fo2) + (0.0718P)2 + 0.1066P] where P = (Fo2 + 2Fc2)/3
5148 reflections	(Δ/σ)max < 0.001
238 parameters	Δρmax = 0.22 e Å−3
0 restraints	Δρmin = −0.16 e Å−3

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq
O1	0.00597 (9)	0.00730 (11)	0.29239 (8)	0.0607 (4)
O2	0.11904 (9)	0.35839 (11)	0.32139 (8)	0.0632 (4)
O3	0.35952 (9)	0.74624 (12)	0.39999 (9)	0.0686 (4)
N1	0.14153 (10)	0.12579 (13)	0.41887 (9)	0.0466 (4)
C1	0.10315 (13)	−0.23275 (17)	0.52145 (11)	0.0543 (5)
C2	0.03317 (14)	−0.29008 (17)	0.45329 (12)	0.0599 (6)
C3	−0.00117 (13)	−0.21414 (16)	0.37654 (11)	0.0557 (5)
C4	0.03510 (12)	−0.07513 (15)	0.36568 (10)	0.0464 (5)
C5	0.10653 (11)	−0.01575 (15)	0.43336 (10)	0.0435 (4)
C6	0.13925 (12)	−0.09409 (16)	0.51009 (10)	0.0502 (5)
C7	0.21681 (12)	0.19787 (17)	0.46691 (11)	0.0500 (5)
C8	0.24727 (11)	0.33802 (16)	0.44826 (10)	0.0488 (5)
C9	0.19690 (11)	0.41507 (16)	0.37232 (11)	0.0488 (5)
C10	0.23632 (12)	0.55360 (16)	0.35497 (11)	0.0535 (5)
C11	0.31795 (12)	0.61279 (17)	0.41101 (11)	0.0549 (6)
C12	0.36589 (14)	0.53810 (18)	0.48665 (13)	0.0654 (6)
C13	0.33182 (13)	0.40505 (18)	0.50384 (12)	0.0626 (6)
C14	0.31877 (13)	0.82640 (18)	0.32322 (12)	0.0600 (6)
C15	0.37303 (14)	0.96959 (18)	0.32326 (12)	0.0597 (6)
C16	0.32694 (18)	1.0777 (2)	0.26853 (13)	0.0769 (8)
C17	0.3757 (2)	1.2105 (2)	0.26580 (14)	0.0893 (9)
C18	0.4695 (2)	1.2378 (2)	0.31800 (16)	0.0918 (10)
C19	0.51594 (18)	1.1327 (2)	0.37257 (18)	0.0933 (9)
C20	0.46785 (16)	0.9979 (2)	0.37561 (16)	0.0781 (8)
C21	0.13941 (16)	−0.3163 (2)	0.60556 (13)	0.0792 (8)
H1o	−0.0411 (17)	−0.044 (2)	0.2490 (16)	0.101 (7)*
H2	0.00830	−0.38330	0.45937	0.0719*
H1n	0.1091 (14)	0.1794 (19)	0.3701 (13)	0.075 (6)*
H3	−0.04862	−0.25606	0.33208	0.0668*
H6	0.18647	−0.05266	0.55491	0.0603*
H7	0.2525 (13)	0.1493 (17)	0.5192 (12)	0.065 (5)*
H10	0.20650	0.60482	0.30510	0.0642*
H12	0.42068	0.58043	0.52442	0.0785*
H13	0.36443	0.35558	0.55341	0.0750*
H14A	0.24242	0.84004	0.32335	0.0720*
H14B	0.33057	0.77387	0.26933	0.0720*
H16	0.26261	1.06082	0.23328	0.0922*
H17	0.34437	1.28183	0.22815	0.1070*
H18	0.50154	1.32764	0.31634	0.1101*
H19	0.57997	1.15094	0.40792	0.1119*
H20	0.49987	0.92686	0.41309	0.0937*
H21A	0.10696	−0.40980	0.60202	0.1186*
H21B	0.11862	−0.26601	0.65674	0.1186*
H21C	0.21574	−0.32628	0.61143	0.1186*

	U11	U22	U33	U12	U13	U23
O1	0.0764 (8)	0.0485 (6)	0.0514 (7)	−0.0042 (5)	−0.0186 (6)	0.0026 (5)
O2	0.0626 (7)	0.0505 (6)	0.0687 (8)	−0.0121 (5)	−0.0277 (6)	0.0067 (5)
O3	0.0682 (7)	0.0572 (7)	0.0771 (9)	−0.0194 (6)	−0.0061 (6)	−0.0054 (6)
N1	0.0481 (7)	0.0460 (7)	0.0435 (7)	0.0016 (5)	−0.0050 (6)	−0.0001 (6)
C1	0.0591 (10)	0.0511 (9)	0.0523 (9)	0.0110 (7)	0.0047 (8)	0.0065 (7)
C2	0.0691 (10)	0.0415 (8)	0.0684 (11)	0.0006 (7)	0.0041 (9)	0.0038 (8)
C3	0.0612 (10)	0.0449 (8)	0.0580 (10)	−0.0016 (7)	−0.0066 (8)	−0.0057 (7)
C4	0.0490 (8)	0.0436 (8)	0.0448 (8)	0.0055 (6)	−0.0029 (7)	−0.0017 (6)
C5	0.0430 (7)	0.0412 (7)	0.0456 (8)	0.0057 (6)	0.0019 (6)	−0.0023 (6)
C6	0.0502 (9)	0.0533 (9)	0.0457 (9)	0.0052 (7)	−0.0014 (7)	0.0000 (7)
C7	0.0501 (9)	0.0538 (9)	0.0436 (9)	0.0020 (7)	−0.0060 (7)	−0.0022 (7)
C8	0.0449 (8)	0.0508 (8)	0.0487 (9)	−0.0029 (7)	−0.0041 (7)	−0.0059 (7)
C9	0.0426 (8)	0.0482 (8)	0.0529 (9)	−0.0017 (6)	−0.0063 (7)	−0.0075 (7)
C10	0.0517 (9)	0.0491 (8)	0.0569 (10)	−0.0032 (7)	−0.0069 (7)	−0.0011 (7)
C11	0.0484 (9)	0.0501 (9)	0.0650 (11)	−0.0082 (7)	0.0013 (8)	−0.0106 (8)
C12	0.0581 (10)	0.0642 (11)	0.0682 (11)	−0.0130 (8)	−0.0182 (9)	−0.0096 (9)
C13	0.0612 (10)	0.0634 (10)	0.0576 (10)	−0.0062 (8)	−0.0178 (8)	−0.0039 (8)
C14	0.0588 (10)	0.0554 (9)	0.0659 (11)	−0.0070 (8)	0.0075 (9)	−0.0090 (8)
C15	0.0650 (11)	0.0543 (9)	0.0630 (11)	−0.0093 (8)	0.0210 (9)	−0.0150 (8)
C16	0.1016 (15)	0.0646 (12)	0.0650 (12)	−0.0107 (11)	0.0122 (11)	−0.0092 (10)
C17	0.140 (2)	0.0627 (12)	0.0685 (14)	−0.0114 (13)	0.0257 (14)	−0.0049 (10)
C18	0.127 (2)	0.0675 (13)	0.0879 (17)	−0.0338 (13)	0.0433 (15)	−0.0139 (12)
C19	0.0841 (15)	0.0798 (15)	0.1170 (19)	−0.0316 (12)	0.0161 (14)	−0.0185 (14)
C20	0.0707 (12)	0.0616 (11)	0.1026 (16)	−0.0153 (9)	0.0123 (11)	−0.0092 (10)
C21	0.0904 (14)	0.0737 (12)	0.0710 (13)	0.0068 (10)	−0.0014 (11)	0.0239 (10)

O1—C4	1.357 (2)	C15—C20	1.379 (3)
O2—C9	1.287 (2)	C15—C16	1.384 (3)
O3—C11	1.365 (2)	C16—C17	1.382 (3)
O3—C14	1.419 (2)	C17—C18	1.366 (4)
O1—H1o	0.96 (2)	C18—C19	1.364 (3)
N1—C5	1.413 (2)	C19—C20	1.396 (3)
N1—C7	1.310 (2)	C2—H2	0.9300
N1—H1n	0.940 (19)	C3—H3	0.9300
C1—C6	1.385 (2)	C6—H6	0.9300
C1—C21	1.508 (3)	C7—H7	0.971 (17)
C1—C2	1.380 (3)	C10—H10	0.9300
C2—C3	1.378 (2)	C12—H12	0.9300
C3—C4	1.387 (2)	C13—H13	0.9300
C4—C5	1.393 (2)	C14—H14A	0.9700
C5—C6	1.385 (2)	C14—H14B	0.9700
C7—C8	1.396 (2)	C16—H16	0.9300
C8—C13	1.421 (2)	C17—H17	0.9300
C8—C9	1.433 (2)	C18—H18	0.9300
C9—C10	1.416 (2)	C19—H19	0.9300
C10—C11	1.369 (2)	C20—H20	0.9300
C11—C12	1.408 (3)	C21—H21A	0.9600
C12—C13	1.344 (2)	C21—H21B	0.9600
C14—C15	1.497 (3)	C21—H21C	0.9600
C11—O3—C14	117.87 (13)	C18—C19—C20	120.3 (2)
C4—O1—H1o	111.1 (13)	C15—C20—C19	120.28 (19)
C5—N1—C7	127.71 (13)	C1—C2—H2	119.00
C5—N1—H1n	119.9 (11)	C3—C2—H2	119.00
C7—N1—H1n	112.4 (11)	C2—C3—H3	120.00
C2—C1—C6	117.40 (15)	C4—C3—H3	120.00
C2—C1—C21	121.94 (15)	C1—C6—H6	119.00
C6—C1—C21	120.67 (15)	C5—C6—H6	119.00
C1—C2—C3	122.37 (15)	N1—C7—H7	116.6 (10)
C2—C3—C4	119.94 (15)	C8—C7—H7	118.9 (10)
C3—C4—C5	118.58 (14)	C9—C10—H10	120.00
O1—C4—C3	124.00 (14)	C11—C10—H10	120.00
O1—C4—C5	117.41 (13)	C11—C12—H12	120.00
N1—C5—C4	116.40 (13)	C13—C12—H12	120.00
N1—C5—C6	123.29 (13)	C8—C13—H13	119.00
C4—C5—C6	120.31 (13)	C12—C13—H13	119.00
C1—C6—C5	121.40 (14)	O3—C14—H14A	110.00
N1—C7—C8	124.48 (15)	O3—C14—H14B	110.00
C9—C8—C13	118.89 (14)	C15—C14—H14A	110.00
C7—C8—C9	121.29 (14)	C15—C14—H14B	110.00
C7—C8—C13	119.80 (14)	H14A—C14—H14B	108.00
O2—C9—C8	120.49 (13)	C15—C16—H16	120.00
O2—C9—C10	121.57 (14)	C17—C16—H16	120.00
C8—C9—C10	117.93 (14)	C16—C17—H17	120.00
C9—C10—C11	120.54 (15)	C18—C17—H17	120.00
C10—C11—C12	121.43 (15)	C17—C18—H18	120.00
O3—C11—C12	114.26 (14)	C19—C18—H18	120.00
O3—C11—C10	124.31 (15)	C18—C19—H19	120.00
C11—C12—C13	119.45 (16)	C20—C19—H19	120.00
C8—C13—C12	121.72 (16)	C15—C20—H20	120.00
O3—C14—C15	110.09 (14)	C19—C20—H20	120.00
C14—C15—C16	119.02 (16)	C1—C21—H21A	109.00
C14—C15—C20	122.43 (16)	C1—C21—H21B	109.00
C16—C15—C20	118.55 (17)	C1—C21—H21C	109.00
C15—C16—C17	120.6 (2)	H21A—C21—H21B	109.00
C16—C17—C18	120.52 (19)	H21A—C21—H21C	109.00
C17—C18—C19	119.73 (19)	H21B—C21—H21C	109.00
C14—O3—C11—C10	−3.0 (2)	C7—C8—C9—C10	−176.46 (14)
C14—O3—C11—C12	177.39 (14)	C13—C8—C9—O2	−178.95 (14)
C11—O3—C14—C15	179.43 (14)	C13—C8—C9—C10	1.8 (2)
C7—N1—C5—C4	−171.50 (15)	C7—C8—C13—C12	177.89 (16)
C7—N1—C5—C6	8.9 (2)	C9—C8—C13—C12	−0.4 (2)
C5—N1—C7—C8	179.88 (14)	O2—C9—C10—C11	178.81 (15)
C6—C1—C2—C3	−0.4 (3)	C8—C9—C10—C11	−1.9 (2)
C21—C1—C2—C3	179.41 (16)	C9—C10—C11—O3	−178.96 (14)
C2—C1—C6—C5	0.0 (2)	C9—C10—C11—C12	0.7 (2)
C21—C1—C6—C5	−179.84 (15)	O3—C11—C12—C13	−179.54 (15)
C1—C2—C3—C4	0.3 (3)	C10—C11—C12—C13	0.8 (3)
C2—C3—C4—O1	179.74 (15)	C11—C12—C13—C8	−0.9 (3)
C2—C3—C4—C5	0.3 (2)	O3—C14—C15—C16	−163.21 (16)
O1—C4—C5—N1	0.2 (2)	O3—C14—C15—C20	17.1 (2)
O1—C4—C5—C6	179.81 (14)	C14—C15—C16—C17	−178.97 (18)
C3—C4—C5—N1	179.66 (14)	C20—C15—C16—C17	0.7 (3)
C3—C4—C5—C6	−0.7 (2)	C14—C15—C20—C19	179.30 (19)
N1—C5—C6—C1	−179.83 (14)	C16—C15—C20—C19	−0.4 (3)
C4—C5—C6—C1	0.6 (2)	C15—C16—C17—C18	−0.9 (3)
N1—C7—C8—C9	−0.4 (2)	C16—C17—C18—C19	0.7 (4)
N1—C7—C8—C13	−178.58 (15)	C17—C18—C19—C20	−0.3 (4)
C7—C8—C9—O2	2.8 (2)	C18—C19—C20—C15	0.2 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1n···O2	0.94 (2)	1.83 (2)	2.609 (2)	138.7 (16)
O1—H1o···O2i	0.96 (2)	1.63 (2)	2.590 (2)	176.1 (17)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1n⋯O2	0.94 (2)	1.83 (2)	2.609 (2)	138.7 (16)
O1—H1o⋯O2i	0.96 (2)	1.63 (2)	2.590 (2)	176.1 (17)

Symmetry code: (i) .